Water Parameters

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    Physicochemical Parameters of Natural Waters

    Written by Keith BellinghamStevens Water Monitoring Systems, Inc.

    http://www.stevenswater.com

     

     Introduction

    All freshwater bodies are interconnected to the oceans, the atmosphere, and aquifers via acomplex hydrological cycle. Wetlands, icecaps and biopheric water also participate in the

    continuous conveyance of water on planet Earth. The Earth’s hydrological cycle is

    driven by evaporation and gravity on which ecosystems and human societies depend.Growing populations may put stresses on natural waters by impairing both the quality ofthe water and the hydrological budget.

    The fate and transport of many anthropogenic pollutants are determined by not only

    hydrological cycles, but also physicochemical processes. In order to mitigate the impact

    human societies have on natural waters, it is becoming increasingly important toimplement comprehensive monitoring regimes. Monitoring water resources will quantify

    water quality, identify impairments, and help policy makers make land use decisions that

    will not only preserve natural areas, but improve the quality of life. Discuss in this articleare in-situ environmental parameters that can be measured remotely by deployable

    sensors.

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    Contents

     pH … 3

    Dissolved Oxygen … 4

    Electrical Conductivity … 5

    Temperature … 7Turbidity … 8

    Total Nitrogen … 8

     Nitrate … 9Ammonia … 10

    Ammonium … 11Phosphate … 11

    Total Phosphorus … 12

    Oxidation Reduction Potential … 14Consequences of Water Quality Problems and Poor Policies … 16

    Conclusion … 17

    References … 17

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     pH

    The pH of natural water can provide important information about many chemical and

     biological processes and provides indirect correlations to a number of different

    impairments. The pH is the measurement of the acid/base activity in solution, specifically

    it is the negative common logarithm of the activity/concentration of hydrogen ions;

     pH = -log[H+]

    In natural waters, the pH scale runs from 0 to 14. A pH value of 7 is neutral; a pH less

    than 7 is acidic and greater than 7 represents base saturation or alkalinity.

    Pure water free of dissolved gases will naturally become ionized;

    H2O H+  + OH

    -

    The actual number of water molecules that will ionize is relatively very small with theamount of hydrogen ions [H+] being equal to the amount hydroxide ion [OH

    -]. At room

    temperature the concentration of [H+] in pure water will be 1 x 10

    -7 moles per liter. A pH

    of 7 is neutral because the –log(1 X 10-7

    ) is 7 by definition.

    In unpolluted or pure waters, the pH is governed by the exchange of carbon dioxide withthe atmosphere. Carbon dioxide is soluble in water and the amount of CO2  that will

    dissolve in the water will be a function of temperature and the concentration of CO2  in

    the air. As the gaseous CO2  becomes aqueous, the CO2  will be converted into H2CO3 which will acidify the water to a pH of about 6. If any alkaline earth metals such as

    sodium are present, the carbonates and bicarbonate formed from the solublization of CO2 

    will interact with sodium increasing the alkalinity shifting the pH up over 7.

    Lower values in pH are indicative of high acidity, which can be caused by the deposition

    of acid forming substances in precipitation. A high organic content will tend to decrease

    the pH because of the carbonate chemistry. As microorganisms break down organicmaterial, the by product will be CO2  that will dissolve and equilibrate with the water

    forming carbonic acid (H2CO3). Other organic acids such as humic and fluvic acid can

    also result from organic decomposition.

    In addition to organic acids and the carbonate chemistry, the acidity of natural waters

    could also be controlled by mineral acids produced by the hydrolyses of salts of metalssuch as aluminum and iron.

    Most metals will become more soluble in water as the pH decreases. For example, sulfur

    in the atmosphere from the burning of coal will create acid rain. The acid rain willdissolve metals such as copper, lead, zinc and cadmium as the rain runs off of man made

    structures and into bodies of water. The excesses of dissolved metals in solution will

    negatively affect the health of the aquatic organisms.

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    The alkalinity of natural waters is controlled by the concentration of hydroxide and

    represented by a pH greater than 7. This is usually an indication of the amount ofcarbonates, and bicarbonates that shift the equilibrium producing [OH

    -]. Other

    contributors to an alkaline pH include boron, phosphorous, nitrogen containing

    compounds and potassium

    Changes in pH can be indicative of an industrial pollutant, photosynthesis or the

    respiration of algae that is feeding on a contaminant. Most ecosystems are sensitive to

    changes in pH and the monitoring of pH has been incorporated into the environmentallaws of most industrialized countries.

     pH is typically monitored for assessments of aquatic ecosystem health, recreationalwaters, irrigation sources and discharges, live stock, drinking water sources, industrial

    discharges, intakes, and storm water runoff.

    Stevens Products for pH Measurement:

    Single Parameter Sensors:  Greenspan pH 100/1200 - 4-20mA or SDI-12 output  Greenspan pH 300 – RS 232 output

    Multi-parameter Sensors:  Greenspan CS 304 (pH, conductivity, temperature, and DO) – RS 232 output

      Greenspan CS4-1200 (pH, conductivity, temperature, and DO) - SDI-12 output  Greenspan CTDP 300/1200 (pH, conductivity, temperature, and depth) – SDI-12

    or RS 232 output

    Analyzers for automated in-field sample collection and analysis

     

    Greenspan Aqualab Analyzer Basis   Greenspan Mini-Analyzer  

     Dissolved Oxygen

    Dissolved oxygen (DO) is essential to all forms of aquatic life including the organisms

    that break down man-made pollutants. Oxygen is soluble in water and the oxygen that isdissolved in water will equilibrate with the oxygen in atmosphere. Oxygen tends to be

    less soluble as temperature increases. The DO of fresh water at sea level will range from

    15 mg/l at 0o C to 8mg/l at 25o C. Concentrations of unpolluted fresh water will be closeto 10 mg/l.

    In general, the concentration of dissolved oxygen will be the result of biological activity.Photosynthesis of some aquatic plants will increase the DO during day light hours and the

    DO levels will fall during the nighttime hours. In natural waters, man-made

    contamination, or natural organic material will be consumed by microorganisms.

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    As this microbial activity increases, oxygen will be consumed out of the water by the

    organisms to facilitate their digestion process. The water that is near the sediment will bedepleted of oxygen for this reason.

    In waters contaminated with fertilizers, suspended material, or petroleum waste,

    microorganisms such as bacteria will break down the contaminants. The oxygen will beconsumed and the water will become anaerobic. Typically DO levels less than 2 mg/l

    will kill fish.

    In situ DO sensors are usually membrane electrodes while laboratory methods are

    titrations.

    Other indirect laboratory tests for assessing the DO is the biological oxygen demand

    (BOD) and the chemical oxygen demand (COD). The BOD is the amount of oxygen

    required to biologically break down a contaminant and the COD is the amount of oxygenthat will be consumed directly by an oxidizing chemical contaminant.

    Stevens Products for Dissolved Oxygen Measurement:

    Single Parameter Sensors:

      Greenspan DO 100/1200 - 4-20mA or SDI-12 output  Greenspan DO 300 – RS 232 output

    Multi-parameter Sensors:  Greenspan CS 304 (pH, conductivity, temperature, and DO) – RS 232 output  Greenspan CS4-1200 (pH, conductivity, temperature, and DO) - SDI-12 output  Greenspan CS 305 (conductivity, temperature, pressure, and DO) – RS 232 output

    Analyzers for automated in-field sample collection and analysis  Greenspan Aqualab Analyzer Basis   Greenspan Mini-Analyzer  

     Electrical Conductivity

    Electrical conductivity (EC) in natural waters is the normalized measure of the water’sability to conduct electric current. This is mostly influenced by dissolved salts such as

    sodium chloride and potassium chloride. The common unit for electrical conductivity is

    Siemens per meter (S/m). Most freshwater sources will range between 0.001 to 0.1 S/m.

    The source of EC may be an abundance of dissolved salts due to poor irrigation

    management, minerals from rain water run off, or other discharges.

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    EC is also the measure of the water quality parameter “Total Dissolved Solids” (TDS) or

    salinity. At about 0.3 S/m is the point as which the health of some crops and fresh wateraquatic organisms will to be affected by the salinity.

    Field measurements of EC reflect the amount of total dissolved solids (TDS) in natural

    waters. The relationship between TDS and EC can be described by the equation;

    TDS (mg/L) ≈ EC (mS/cm) X 640

    Salinity refers to the presence of dissolved inorganic ions such as Mg++

    , Ca++

    , K +, Na

    +,

    Cl-, SO2

    4-, HCO3

    -  and CO3

    2-  in the aqueous solution or soil matrix. The salinity is

    quantified as the total concentration of soluble salts and is expressed in terms of electricalconductivity. There exists no in-situ salinity probe (based on EC alone) that can

    distinguish between the different ions that may be present. When salts such as sodium

    chloride are in their solid form, they exist as crystals. Within the salt crystal, the sodiumand the chorine atoms are joined together in what is called an ionic chemical bond. An

    ionic chemical bond holds the atoms tightly together because the sodium atom will giveup an electron to the chlorine thus ionizing the atoms. If an atom like sodium gives up an

    electron, it is said to be a positively charged ion (also called a cation). If an atom such aschlorine receives an electron, it is said to be a negatively charged ion (also called an

    anion and is given the suffix ide, like chloride). The sodium and the chloride ions

    comfortably arrange themselves into a stacked like configuration called a crystal lattice.The sodium chloride crystal lattice has a zero net charge.

    Water will dissolve the sodium chloride crystal lattice and physically separate the twoions. Once in solution, the sodium ion and the chloride ion will float around in the

    solution separately and randomly. This is generally true for all inorganic salts. Once in asolution, the ions will float apart and become two separate species dissolved in the water.

    Typical, charged ions exist separately in a solution. If the water dries up, the cations and

    the anions will find each other and fuse back into a crystal lattice with a zero net charge.

    Stevens Products for Electrical Conductivity Measurement:

    Single Parameter Sensors:  Greenspan EC 250/1200 - 4-20mA or SDI-12 output

      Greenspan EC 350 – RS 232

    Multi-parameter Sensors:

      Greenspan CS 304 (pH, conductivity, temperature, and DO) – RS 232 output 

    Greenspan CS4-1200 (pH, conductivity, temperature, and DO) - SDI-12 output  Greenspan CS 305 (conductivity, temperature, pressure, and DO) – RS 232 output

    Analyzers for automated in-field sample collection and analysis 

    Greenspan Aqualab Analyzer Basis 

      Greenspan Mini-Analyzer  

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    Temperature

    Many aquatic organisms are sensitive to changes in water temperature. Temperature is an

    important water quality parameter and is relatively easy to measure. Water bodies will

    naturally show changes in temperature seasonally and daily; however, man made changes

    to stream water temperature will affect fish’s ability to reproduce. Many lake and riverswill exhibit vertical temperature gradients as the sun will warm the upper water while

    deeper water will remain cooler.

    Fish friendly dams will have selective water releases where the temperature of the stream

    can be controlled by the water depth of release. In the summer, the water could be

    released from the bottom of the dam and in the winter the water is released from the top.This selective release will mitigate the impact the dam will have on the water

    temperature.

    Some streams will increase in temperature as the stream water moves down stream

    through urban, industrial and agricultural areas. This man made temperature loading can be characterized by the Total Maximum Daily Load (TMDL). For example, a stream in

    forested head waters will be at a suitable temperature for the native aquatic life. As thestream meanders through pasture land, the riparian vegetation will not be abundant

    enough to effectively shade the stream. Once the stream makes in to urban area, the

    stream may become channeled to make room for housing. Removing the natural meanderfrom a stream will increase the velocity of the water which will cause erosion further

    degrading the quality of the water. Impervious structures such as parking lots, roads and

     buildings will prevent the infiltration of rainwater into the groundwater. Instead of beingfed from cool groundwater, the stream will receive run off after rain events further

    degrading the quality of the water and increasing the temperature.

    Environmental policies require the monitoring of stream water temperature. In most

    urban and industrial locations, environmental permits are required to help minimize thetemperature loading to streams.

    Stevens Products for Temperature Measurement:

    Multi-parameter Sensors:

      Greenspan CS 304 (pH, conductivity, temperature, and DO) – RS 232 output  Greenspan CS4-1200 (pH, conductivity, temperature, and DO) - SDI-12 output  Greenspan CS 305 (conductivity, temperature, pressure, and DO) – RS 232 output

    Analyzers for automated in-field sample collection and analysis  Greenspan Aqualab Analyzer Basis 

      Greenspan Mini-Analyzer  

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    Turbidity

    Turbidity or Total Suspend Solids (TSS) is the material in water that affects the

    transparency or light scattering of the water. The measurement unit used to describe

    turbidity is Nephelometric Turbidity Unit (NTU). The range for natural water is 1 to 2000

     NTU. There are a number of manual field methods for measuring TSS, such as Secchidiscs where a metal disc is lowered in the water with a calibration line. The depth at

    which the disc disappears is directly correlated to TSS. In situ electronic turbidity sensors

    measure the backscatter of infrared light to determine the NTU of the water.

    TSS is typically composed of fine clay or silt particles, plankton, organic compounds,

    inorganic compounds or other microorganisms. These suspended particles range in sizefrom 10 nm to 0.1 mm although in standardized laboratory tests, TSS is defined as the

    material that cannot pass through a 45 μm diameter filter. TSS as well as TDS can be

    influenced by changes in pH. Changes in the pH will cause some of the solutes to precipitate or will affect the solubility of the suspended mater.

    The manmade sources of TSS include erosion, storm water runoff, industrial discharges,

    microorganisms, and eutrophication. Many fish species are sensitive to prolongedexposure to TSS and monitoring of TSS is an important criteria for assessing the quality

    of water.

    Stevens Products for Turbidity Measurement:

    Single Parameter Sensors:  Greenspan TS 100/1200 - 4-20mA or SDI-12 output  Greenspan TS 300 – RS 232 output

    Analyzers for automated in-field sample collection and analysis  Greenspan Aqualab Analyzer Basis   Greenspan Mini-Analyzer  

    Total Nitrogen

     Nitrogen (N2) is essential to life on Earth and is the most abundant element in Earth’satmosphere. Biological compounds such as proteins, amino acids, and nucleic acids

    contain nitrogen. In the environment, plants and micro organisms convert N2  into a

    different oxidation states where it becomes part of the nitrogen cycle. The majorinorganic oxidation states include nitrate ion (NO3

    - ), nitrite ion (NO2

    -), ammonia (NH3),

    and ammonium ion (NH4-). Total nitrogen in natural waters refers to the sum of organic

    nitrogen containing compounds, and the inorganic nitrogen oxidation states present insolution. Total nitrogen can be calculated from the sum of the total kjeldahl nitrogen

    (organic and reduced nitrogen) ammonia, nitrate and nitrite. Acceptable ranges of total

    nitrogen are 2 to 6 mg/L.

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    There are many sources of total nitrogen in the environment. Automobile exhaustcontains nitrous oxide which will enter surface water through precipitation processes.

    Storm water runoff, livestock, sewage discharge, fertilizers and waste water discharges

    all contribute to the abundance of total nitrogen in the environment. Natural sources are

    the natural break down of plant and animal material.

    Stevens Products for Total Nitrogen Measurement:

    Analyzers for automated in-field sample collection and analysis

      Greenspan Aqualab Analyzer Basis   Greenspan Mini-Analyzer  

     Nitrate

     Nitrate ion (NO3-) is the common form of nitrogen in natural waters. Nitrite (NO2

    -) will

    oxidize into nitrate after entering an aerobic regime.

     NO2- + H2O NO3

    -  + 2 H

    +

     Similarly, plants and microorganisms will reduce nitrate into nitrite but nitrite ion will

    quickly oxidizes back into nitrate once it reenters the water. Natural sources of nitrate

    are igneous rock, plant decay and animal debris. Nitrate levels over 5 mg/L in naturalwaters normally indicates man made pollution, 200 mg/L is an extreme level. Man made

    sources of include, fertilizers, livestock, urban runoff, septic tanks, and waste water

    discharges. In general, nitrates are less toxic to people than ammonia or nitrite however athigh levels nitrate will become toxic especially to infants. Methemoglobinemia is nitrate

     poisoning where high levels of nitrate enter in hemoglobin will oxidize the ferric iron II

    into ferrous iron III inhibiting the blood’s ability to carry oxygen.

    In the environment, nitrate will become toxic to fish at about 30 mg/L. Nitrate pollution

    will cause eutrophication of a stream where algae and aquatic plant growth will consume

    the oxygen and increase the TSS of the water. Eutrophication is usually the result ofnitrate and phosphate contamination and is a significant reduction of water quality.

     Nitrate can exist naturally in groundwater but can increase dramatically on irrigated landsif the irrigation operation is not managed properly. Groundwater contaminated with

    nitrate can contaminate sources of drinking water in wells, and will contaminate the

    surface water as the ground water recharges streams and lakes. As more land is converted

    into agricultural land and as urban areas expand, nitrate monitoring is an important tool inaccessing locating and mitigating man made sources of nitrate.

    Stevens Products for Nitrate Measurement:

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    Analyzers for automated in-field sample collection and analysis  Greenspan Aqualab Analyzer Basis 

      Greenspan Mini-Analyzer  

     Ammonia

    In unpolluted water, trace amounts of ammonia (NH3) are present from the reduction of

    atmospheric nitrogen by aquatic microorganisms;

     N2(g) + 3H2 (g) 2NH3(aq)

    Ammonia also occurs naturally from the breakdown of nitrogenous organic compoundsin water and soil and the breakdown of biota. Ammonia is at equilibrium with ammonium

    ion (NH4+

    ) and the equilibrium reaction between ammonia and ammonium ion (seeammonium) is pH dependent.

     NH3(aq) + H+(aq) NH4

    + (aq) + OH

    -(aq)

    At a higher pH, ammonia will be the predominate form and at a lower pH the ammonia

    ion will be predominate. Total ammonia is the sum of the two forms. Unionized ammoniais much more volatile than the ionized form, as the pH increases, NH3  will leave the

    aqueous solution by volatilization. Natural seasonal fluctuations can occur from the death

    and decay of phytoplankton, bacteria and other aquatic organisms. The bottom anoxic

    waters of lakes may contain higher levels of ammonia as the decay material settles to the bottom.

     Natural unpolluted waters can be 0 to 3 mg/L. Higher concentrations correspond to pollution and can be toxic to aquatic organisms. Man made sources of ammonia can

    come from industrial discharges, particularly from the pulp and paper industry.

    Other made man sources of ammonia include fertilizer runoff, sewage releases into

    natural waters, and industrial releases.

    Stevens Products for Ammonia Measurement:

    Analyzers for automated in-field sample collection and analysis 

    Greenspan Aqualab Analyzer Basis   Greenspan Mini-Analyzer  

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     Ammonium

    Ammonium (NH4+) is the ionized form of ammonia and will equilibrate with ammonia in

    solution (see ammonia). The source of ammonium in the environment mirror that of

    ammonia at a pH of less 8, over 95% of the total ammonia is in the ammonium ion form

    at 15 degrees Celsius. Most vertebrates including mammals will convert ammonium intourea where it can be excreted or bioaccumulated.

    Ammonium can be measured in situ with an ion selective electrode. Ammonium ion isless toxic than ammonia and because it is the most abundant form at the typical pH of

    surface water. Ammonium ion will however become toxic at higher concentrations.

    Stevens Products for Ammonium Measurement:

    Analyzers for automated in-field sample collection and analysis  Greenspan Aqualab Analyzer Basis 

     

    Greenspan Mini-Analyzer  

     Phosphate

    Phosphate (orthophosphate or total reactive phosphorus [TRP]) is the ionized form of

    Orthophosphoric acid. In solution and in natural waters, phosphate ion will have many

    forms and will be at a pH dependent equilibrium;

    H3PO4  H+ + H2PO4

    -

    H2PO

    4

    -  H

    + +HPO

    4

    2-

    HPO42-

      H++PO4

    3-

    The higher the pH, the more PO43-

     will form from the deprotination of HPO42-

    .Unlike total ammonia, phosphates are less soluble and less volatile, therefore, phosphates

    will form salts with sodium and calcium and fall out of solution to accumulate in the

    sediment. Phosphates ions in natural waters will exist in solution in its ionized form, as

    salts, in organic form or as a particulate species. Higher concentrations rarely occur, because after it enters a water system, it will be rapidly up taken by plants.

    In general, phosphorous is an essential nutrient to living organisms (see total phosphorus). In unpolluted waters, phosphorous can enter a water system from the

    weathering of phosphorous baring rocks and minerals. In areas of high volcanic activity,

     phosphorous may be naturally abundant in the soils.

    Man made sources of phosphate in the environment include domestic and industrial

    discharges, agricultural runoff where fertilizers are used, and changes in land use in areaswhere phosphorous is naturally abundant in the soil.

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    In general, phosphates are not very toxic to people or other living organisms. Like

    nitrogen containing compounds, the main environmental impact associated with phosphate pollution is eutrophication. High levels of phosphorus will be quickly

    consumed by plant and microorganisms, impairing the water by depleting the dissolved

    oxygen and increasing the turbidities. These impairments will kill or harm fish and other

    aquatic organisms.

    In the late 1970’s, phosphates were phased out of domestic detergents. Prior to the

    removal of phosphates, domestic sewerage would cause very large algal blooms in lakes,rivers and streams.

    Stevens Products for Phosphate Measurement:

    Analyzers for automated in-field sample collection and analysis  Greenspan Aqualab Analyzer Basis   Greenspan Mini-Analyzer  

    Total Phosphorus

    The term “total phosphorus” corresponds to the total dissolved and filterable phosphorus

    in all of its forms in solution including organic phosphorus. Like phosphates, the major

    environmental impact associated with the total phosphorus parameter is eutrophication ofsurface water (see phosphate). The total phosphorus parameter may be chosen over

     phosphates because in most water systems, the total phosphorus concentration correlateswell to other water quality parameters particularly algae growth and chlorophyll.

    Some organic forms of phosphorus are relatively unreactive and would not be detected byan analyses for phosphates. Organic phosphorus can dramatically affect the algal growth;

    therefore, it may be more appropriate to evaluate total phosphorus as opposed to the

    reactive phosphates. Some microorganisms will uptake only inorganic phosphates; in this

    case, measurement of reactive phosphates may be a better indicator of water quality thantotal phosphorus. Ideally, phosphates and total phosphorus should both be evaluated

    when assessing a water system.

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     Eutrophication from phosphorus contamination (photo provided by the US EPA)

    The fate and transport of phosphorus and phosphorus containing compounds in the

    environment is driven by the phosphorus cycle. The phosphorus cycle is primary driven

     by the uptake of phosphorus by living organisms. Phosphorus and phosphorus containing

    compounds act as energy conveyers for living organisms. Once the organism dies, phosphorus will be reintroduced to the soil and water where it is up taken again by

    another organism. The residence time in any particular body of water will be a function

    of pH, temperature, and climate. The most common source of phosphate pollution is poormanagement of agricultural irrigation and run off.

    Orthophosphate ester (organic phosphate). Where R can be an organic radical or H.

    Stevens Products for Total Phosphorus Measurement:

    Analyzers for automated in-field sample collection and analysis 

    Greenspan Aqualab Analyzer Basis   Greenspan Mini-Analyzer  

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    Oxidation Reduction Potential

    Oxidation reduction potential (ORP) or redox is the activity or strength of oxidizers or

    reducers in solution. ORP measurements are used to quantify water disinfection

     procedures and access breakdown of pollutants. Like pH, ORP is not the direct

    concentration measurement of the analyte, but the activity. The common unit for ORP ismillivolts. If the potential is positive, than the solution is oxidizing where as a negative

    ORP is a reducing solution. The more positive, the greater the affinity for electrons.

    Reduction/oxidation (redox) reactions are electrochemical reactions that involve the

    migration of electrons from one species to another. An oxidizer is a chemical species that

    receive electrons, and reducers are the chemical species that donate electrons. The table below may provide some useful insight by summarizing the terminology.

    Reducers Oxidizers

    Donate electrons Accept electrons

    Reductants OxidantsGets Oxidized Gets Reduced

     Negative Voltage (or neutral) Positive Voltage (or neutral)

    Reducing Agent Oxidizing Agent

    Sodium sulfite Chlorine

    Sodium bisulfate Ozone

    Hydrogen Sulfide Hydrogen Peroxide

    Like alkalinity and bassisity, one is at the expense of the other. ORP is not measured by

    an absolute direct measurement, but rather it is measured by the comparison to a

    reference redox reaction. By convention, most ORP measurements are based on the

    comparison to a Standard Hydrogen Electrode (SHE) which is arbitrarily assigned to be“0” Volts ORP.

    2H+ + 2e

    -  H2 (g) SHE reaction

    H+ + e

    -  ½ H2 (g) SHE Half Reaction

    In the process of photosynthesis, organic compounds that contain carbon, nitrogen

    and sulfur, will be reduced. Chemical energy is stored in the reduced species which also

    includes organic pollutants. Microorganisms will catalyze the reduced chemical speciesto obtain energy for their metabolism and other cellular processes. Oxygen is the most

    favorable oxidant used by many organisms. To obtain chemical energy, the organism will

    take the electrons away from the reduced chemical species, give it the electron acceptingO2  reducing it to H2O. Other oxidants in natural waters include NO3

    -  and SO4

    2-. The

    dominant organism in a micro–environment will be the organism that can utilize the best

    oxidant available. The best oxidant for the organism will be the one that has the highestORP.

    Many environmental pollutants biodegrade in this fashion and need strong oxidizingagents to facilitate the process. For example, injecting oxygen or an oxygen releasing

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    compound into the groundwater will chemically break down subsurface pollutants such

    as petroleum products and other organic pollutants. In groundwater remediationoperations involving organic pollutant, aerobic and a strongly positive ORP conditions

    need to be achieved.

    Up until the 1970’s, it was common practice for dry cleaners to dump the spent drycleaning solvent on the ground to get rid of it. Dry cleaning solvents contain chlorinated

    solvent that can be extremely toxic to aquatic life and people. Because the chlorinated

    solvents are more dense than water, they will quickly migrate downward to the bedrock.The solvent will slowly solubilize into water where it is then transported to the surface

    water. In some cases, groundwater contaminate plumes will travel many miles over the

    course of many decades before it seeps into a river or lake. Most of the chlorinatedsolvents seeping into water bodies today, were dumped in the 1940s and 50s.

    In chlorinated solvents, the chlorine-carbon chemical bond is very strong and resistant to break down. New remediation techniques for chlorinated compounds involve anaerobic

     process with negative ORPs species such as reduced iron (Fe

    0

      or Fe

    II

    ) These reducingagents will donate electrons to the chlorine atom thus breaking the chlorine carbon

    chemical bond. Once the chemical bond is broken, the chlorinated solvent willchemically degrade into more benign species.

    ORP measurements are useful for drinking water, swimming pools, fruit and vegetabledisinfection, metal etching, waste water treatment and other applications. ORP targets in

    mV can be set to eliminate pathogens such as E. Coli, and other harmful bacteria and

    viruses. An oxidizing chemical species pulls electrons away from cell membranesoxidizing the cell quickly causing death to the pathogen.

    The higher the ORP, the faster the organism will die. For example an ORP of 665 mV

    will kill E. Coli within a few seconds, where as an ORP of 485 will eliminate the E. Coli

    within a day.

    Stevens Products for Oxidation Reduction Potential Measurement:

    Single Parameter Sensors:  Greenspan ORP 100 – 4-20mA output

      Greenspan ORP 300 – RS 232 output

    Analyzers for automated in-field sample collection and analysis

      Greenspan Aqualab Analyzer Basis  

    Greenspan Mini-Analyzer  

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    Consequences of Water Quality Problems and Poor Policies

    Ohio’s Cuyahoga River first caught on fire in the 1930’s and would catch on fire every

    few of years until the late 1960s. In 1969, levels of oil sheen and floating debris got so

     bad that when the river caught on fire it would cause damage to bridges and boats. This

    event lead to environmental reforms in the United States which included the Clean WaterAct, and the formation of the US Environmental Protection Agency.

    The 1952 burning of the Cuyahoga River, Cleveland Ohio. (Photo provided by the US EPA)

    Between 1942 and 1952, the Hooker Chemical Company buried more than 21,000 tons of

    chlorinated benzenes, dioxin tricholophenols and other chemicals into a land fill near

    Love Canel, New York. In 1952, as a gift to the school system, Hooker sold 16 acres ofthe land fill to the local school system for the new elementary school and new homes at a

    reduced price. By 1958 the fumes coming up from the ground were so toxic that it caused

    severe burns, illness, blisters and death. Eventually, the US Federal Government spentmillions of dollars relocating the residents and hundreds of millions of dollars cleaning

    up the site. This environmental disaster ignited many law suits and the creation of

    “Superfund” regulations.

    Perhaps one of the worst environmental events occurred in 1984 in Bhopal, India when

    42 tons of methyl isocyanate was released into the environment, killing over 2,000 people

    and injuring several thousands more. This incident led to the Right to Know Laws andimproved emergency responses in the US and in Europe.

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    Conclusion

    By the late 1970s, many industrialized countries adopted environmental laws prohibiting

    the release of toxic chemicals into the environment. While rivers catching on fire and

    toxic chemicals oozing into elementary schools are largely a thing of the past, the quality

    of natural waters are still being impacted by land use. As populations grow, natural landsare diminishing and are being converted into urbanized land and agricultural land. The

    change in land use from a forest to urbanized land will threaten the water quality of

    natural waters and the ecosystem which is dependent on it.

    One of the most important tools for mitigating human impact to streams, rivers and lakes

    is water monitoring. Monitoring solutions help prevent the introduction of contaminates,indentifies impaired reaches, and helps enforce environmental policies. Monitoring

    regimes, along with progressive environmental policies, are helping to mitigate the

    human impact to natural waters and natural ecosystems to improve the quality of life.

     References

    Pankow, J. F., Aquatic Chemistry Concepts. 1991.

    Schwarzenbach, R. P., P. M. Gschwend, and D. M. Imboden., Environmental OrganicChemistry, 2

    nd Ed. 2003.

    Standard Methods for Examination of Water & Wastewater. American Public HealthAssociation; 20th edition (January 1999).

    US Geological Survey Circular 1139, Ground Water and Surface Water A Single

    Resource.

    Warrick, A. W., Soil Water Dynamics. 2003, Oxford University Press.

    World Heath Organization, Water quality assessments: A guide to the use of biota,

    sediments and water in environmental monitoring, 2nd ed., Edited by Deborah Chapman,

    1996.

    Since 1911 Stevens Water Monitoring Systems has provided deployable instruments and monitoring

    solutions that help protect water and soil resources. Please visit www.stevenswater.com for moreinformation.

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